Addition homopolymers of divinyl carbonates

ABSTRACT

THERE ARE PROVIDED ADDITION HOMOPOLYMERS OF A CARBONATES HAVING THE FORMULA   R1-C(-R2)=C(-R3)-OOC-O-C(-R3)=C(-R1)-R2   WHEREIN R1 R2 AND R3 ARE HYDROGEN, PHENYL OR ALKYL CONTAINING UP TO 20 CARBON ATOMS.

United States Patent US. Cl. 26077.5 UA 3 Claims 2 ABSTRACT OF THE DISCLOSURE There are provided'addition homopolymers of a carbonate having the formula wherein R R and R are hydrogen, phenyl or alkyl containing up to 20 carbon atoms.

This application is a continuation of Ser. No. 591,091, filed Nov. 1', 1966, now abandoned.

This invention relates to novel polymers and is more particularly concerned with polymers of divinyl carbonates.

In the co-pending application Ser. No. 591,094 of David Rhum and George L. Moore, entitled Process for the Preparation of Divinyl Carbonates, now US. Pat. No. 3,574,699, issued Apr. 13, 1971, and being filed con-currently herewith, there are disclosed novel divinyl carbonates of the formula set forth below.

It is an object of this invention to provide novel polymers formed from such monomers.

Thus, in accordance with this invention there are provided polymers of vinyl monomers described in said copending application and which can be represented by the formula When each R is methyl, the compound is diisopropenyl carbonate, having the formula CH CH 'In accordance with this invention, these novel compounds of the Formula 1 are suitably prepared by the reaction of a mercury (II) aldehyde or ketone with phosgene in the presence of a tertiary amine as catalyst, suitrt'n ledigmg ln the'case of divinyl carbonate,

3,651,020 Patented Mar. 21, 1972 this compound is suitably prepared by the reaction of mercury (LI) bis-acetaldehyde with phosgene. The reaction can be represented by the following equation:

To prepare diisopropenyl carbonate, chloro mercury acetone is reacted with phosgene in the above-specified reaction system. To prepare other compounds falling Within the scope of Formula 1, phosgene is reacted with the appropriate chloro mercury ketone.

The reaction proceeds readily at room temperature and at atmospheric pressure and raising or lowering the temperature of the reaction mixture, or raising or lowering the pressure are not necessary. Any inert solvent may be employed but aliphatic ethers or aliphatic or aromatic hydrocarbon solvents, or normally liquid chlorinated hydrocarbons are preferred. Typical aliphatic ethers, which may be cyclic or acyclic, include dioxane, di-isopropyl ether, di-n-butyl ether, and the like, and typical hydrocarbon solvents include pentane, hexane, heptane, cyclohexane, methyl cyclohexane, benzene, toluene, xylene, carbon tetrachloride, and the like. Ordinarily, any inert solvent which is liquid at room temperature can be employed, the solvent suitably being selected so that it can readily be separated from the carbonate by distillation.

=In carrying out the reaction, the mercury compound, solvent and catalyst are first added to the reaction vessel, and the phosgene is then gradually introduced. For the best results, anhydrous conditions are maintained.

The product divinyl carbonate is readily separated from the reaction mixture by distillation. The reagents are preferably used in 1:1 mole ratios but the ratio of mercury compound, e.g. mercury (II) bis-acetaldehyde, to phosgene generally ranges between 1.5:1 to 1:15, although a higher mole ratio, e.g. up to about 3:1 can be employed. The amount of tertiary amine is variable over a wide range, but preferably about one mole of amine per mole of mercury is employed, but ratios can vary in accordance with those specified above, and even beyond.

Any tertiary amine can be employed as catalyst. Typical amines include aliphatic amines such as trimethyl amine, trieth'yl amine, tributyl amine and the like, heterocyclic amines such as pyridine, picoline, quinoline, methyl quinoline, and the like, and aromatic amines such as N,N- dimethyl aniline, N,N-diethyl aniline, and the like.

The following examples, which are given for illustrative purposes only, serve to show the preparation of the divinyl carbonates of this invention and their polymerization.

EXAMPLE I The reactor was a 1 l. resin kettle fitted with a stainless steel stirring shaft and blade, thermometer, gas inlet tube, and a Dry Ice cold finger condenser was connected to a nitrogen T tube which led to a Dry Ice trap and an aqueous Na CO scrubber. Materials used: di-isopropyl ether, freshly distilled-275 ml. N,N-dimethyl aniline ml., .59 mol. mercury bis-acetaldehyde3l3.5 g., 1.1 mol. phosgenel09 g., 78 ml., 1.1 mol.

The mercury bis-acetaldehyde was prepared according to Nesmeyanov, AN, Lutzenko, IF, Khomutox, RM, Izv. Akad.'Nank SSSR 8, 942 (1957).

The reactor was dried by purging with N and heating. After cooling to room temperature, the first 3 materials were charged into the reactor.

The phosgene was first distilled from the cylinder into a calibrated tube, which was cooled in an isopropanol bath at 10 C.,-until the volume desired (78 ml.) had condensed.

Keeping the reaction temperature at about 25 C. by We have found that the ratio of cyclopolymerization to means of a cooling bath, the phosgene was allowed to linear polymerization is a function of both temperature distill from the tube into the gas phase of the reactor from and solvent. The behavior of the pure monomer is shown where it was readily absorbed by the reaction mixture. in Table 1. The phosgene addition time was 4 hrs. The mixture was 5 finally warmed to 58 C. (over a period of 1 /2 hr.), and TABLE I COOlCd. Ratio of Emembered rinlg car- The mixture was filtered, and thebrittle mercury-conh2 3: giiiii-hoi h ivd talnmg sohds were washed wlth dl-lsopropyl ether. The T m 0 C m total dI-ISOPI'OPYI ether filtrate was then Washed with water, 10% sulfuric acid (to remove any free amine present), 33 32 12 5 22 32 37 5% HCO3, and finally water. The di-isopropyl ether g ejjjjj j 32 52 solution was dried over anhyd. Na SO Ethyl acetate. 6.0 32 4 70 The drled solution was next d1st1lled through a column hifiifififiiigtsaid 7 o 51 2( 80 packed with SS Heli-pak. Di-isopropyl ether was first 15 removed at 31-35 Cl 190-80 mm., then the divinyl carbonate distilled at 40.5-43.5 c./7o-7s mm., wt.-77.6 g. Table I also shows the fi t of solvent, on the struc- Conversion (based on 1 mol of mercury bis-acetaldehyde f j of the final P Y at dlffefenf temperatures, and forming 1 mol of divinyl b 61 7% 1t 1s observed that the percent of r ng cychc carbonate Based on vapor chromatography the divinyl carbonate groups 13 fi 1% to 897031116 fi l concentration of was 97-99% pure, monomer 1n the polymerization solutions was 28%.

The above-described monomers can be polymerized to It is thus poss1ble to control the structure of the reform poly(divinylcarbonat s), i ll represented by sultant polymer, polyDVC, and also the structure of the poly(divinylcarbonate) d polywiisopmpenyl ealibom resultant PVA WhlCh may be madefrom polyDVC. 1nce at by using th usual free radical Polymerization tech commerclal PVA made from p0lyvmyl acetate contalnmg niques. Polymers can be formed by bulk, in solution, or 1% f less of L -g Y l l-l lts, Completely new types of e l io l i i T temperature f p1ymeriza polyvinyl alcohols, CODlIfillllIlg up to 90% of the hydroxyl tion can be varied but is most suitably between about gTouPs Y P nil-Its may Prepared at P h 4() d about 150 C f bl and from polyDVC with higher ratios perhaps possible in C. The resulting materials can be precipitated in methanol 30 the ep if they are not initially insoluble in the reaction medium. addlhoh to the prepefatlon 0f y a pp y l' The polymeric products in all cases are white powders. havlng a novel strllehlfe, It has e found that P P In the case of oluti polymerization, any inert Solvent mer possesses deslrable properties, such as belng white can be used, such as ethers, hydrocarbons, chlorinated colorless, being stahle e P being hydrocarbons, and like sol-vents which are liquid under capable of y P i; y Vlrhle of Its uflreaeted y the polymerization conditions, including the solvents listed groups, and helng hydrelylable Furthermore, above for the preparation of monomers. Particularly suit- When being hydrolyzed to PVA, the P y P Y able are the solvents used i th examples b l possesses the desirable property of not, at an intermediate Suitable as catalysts are the oil soluble free-radical Stage of hydrolysis, forming a y' mess and thereby catalysts such as the organic peroxides, e.g. lauroyl per- 40 making difilelllt the completion of hydrolysis- POIYDVC oxide, tert-butyl peroxy pivalate, 2,4-dichlorobenzoyl peris insoluble in the Conventional reaction e m oxide, and benzoyl peroxide, or the azo catalysts such as 1 01, use in the preparation of PVA from polyvinyl esters disclosed in Hunt US. Pat. No. 2,471,959, e.g azD-bis- (in contrast to polyvinyl acetate) and the hydrolysis to isobutyronitrile, which is commercially referred to in the PVA s arr t in a heterogeneous mixture entirely, t as AZNJ? with no agglutination, and enhanced facility.

The structure of the polymers has been determined with the aid of infra-red spectroscopy. It has been shown that EXAMPLE H the polymerization proceeds by both linear and cyclo- 228 g. chloromercuryacetone, 15.5 cc. dimethyl anipolymerization, using respectively, one or both vinyl line, and 400 cc. isopropyl ether were stirred in a threegroups of'the monomer, to produce a polymer having neck 1 liter flask with a C0 condenser, and a gas inlet linear units and cyclic units incorporated inthe backbone. tube connected. The gas inlet tube was attached to at These structural features are shown below: calibrated tube which in turn was connected to a cylinder =0 (B C C (3H2 A g P 2 linear Cyclic unit: Cyclic unit:

unit 5 membered ring 6 membered ring Our studies show that the polymers consist of linear of phosgene. The phosgene was condensed inthe caliunits and 5 membered ring cyclic units with few, if any, brated-tube and distilled into the reaction mixture while 6 membered ring cyclic units detectable. These various stirring. The reaction was then heated to 67 and kept groups may be detected with the aid of infrared spectrosat that temperature for 1 hour, the solid portion becoming copy because each group absorbs light of a diflerent wavevery sticky. On cooling, the solid portion became taflylength. Thus, the 5 membered ring carbonate absorbs at 70 like.

5.55 microns, the 6 membered ring carbonate and the The liquid portion of the reaction mixturetwas filtered, linear carbonate at 5.72 microns, but the linear carbonate and the major portion of the isopropyl'ether'distilledin also has a free vinyl group, absorbing at 6.05 microns, a Vigreux column. The remaining portion'was distilled at absent in the 6 membered ring, by which the former may reduced pressure; the distillate of di-isopropenyl carbe identified. bonate, B.P. 87/95 mm., was submitted for purification by preparative scale gas chromatography and 10.9 g. of 99.4% pure material was isolated. The infrared spectrum of the compound has a band at 5.65;]. for carbonate and 5 .95 for vinyl.

Elemental analysis.Calculated (percent): C, 59.2; H, 7.04. Found (percent): C, 58.72; H, 6.77.

The polymers of this invention have utility for forming molded products, coatings, and the like. The following examples show typical polymerizations.

EXAMPLE III To 1000 ml. of the divinyl carbonate produced in Example I there was added 8.5 mg. of azobis-isobutyronitrile (AZN), and the mixture was heated at 73 in a nitrogen atmosphere. A white, solid, brittle polymer formed in the course of several minutes.

EXAMPLE IV 1 g. of diisopropenyl carbonate and 2 milligrams of 2,2'-azobisisobutyronitrile were degassed and sealed in a glass tube under vacuum and placed in a bath ranging from 550-76 C. for 16 hours. The tube then contained a small amount of insoluble white powder which was filtered and vacuum dried. The infrared spectrum of the white poly(diisopropenyl carbonate) had a strong absorption at 5.60 1, for the carbonate group. The polymer melted at 195-210" to a clear liquid, without decomposition.

EXAMPLE V Two ml. of DVC, 5 ml. of benzene, and 11.4 mg. of AZN, were heated at 76 C. in a sealed tube under vacuum for 2 hr. A white insoluble polymer formed, and after Washing with methanol, 1.00 g. was obtained. An exothermic reaction in the polymer was observed by differential thermal analysis between 265 and 287 C. The infrared spectrum showed AbS 5.55 microns AbSS.SS microns+AbS 5.72 microns 5AbS 6.05 microns AbS 5.55 microns-l-AbS 5.72 microns EXAMPLE VI The procedure in Example V was followed using acetone as the solvent, 20 ring of AZN, and irradiating the polymerization tube with ultraviolet light at C. for 16 hr. 0.40 g. of polyDVC was obtained when the solution was poured into methanol. The infrared analysis showed A 5.55 A 6.05 A 5.55+A 5.72 and A 5.55+A 5.72

EXAMPLE VII The procedure of Example V was followed using dimethylacetamide as solvent, and mg. benzoyl peroxide as initiator at 90 C. for 3 hr. Upon pouring the solution into methanol, 0.85 g. of polyDVC were obtained. The infrared analysis showed The procedure of Example V was followed using tetrahydrofuran as the solvent and 6 mg. of benzoyl peroxide as initiator at 90 C. Shortly after reaching 90, the

solution explosively polymerized to form a granular white product. After washing with methanol, 1.40 g. of polymer were obtained.

A 5.55 A 5.55-l-A 5.72

=O'52 and A 5.55+A 5.72

EXAMPLE IX The poly(divinylcarbonate) prepared as described in Example III was suspended in boiling methanol which contained dissolved sodium, i.e. sodium methoxide. A weight of sodium about 5% of the weight of poly (divinylcarbonate) was used. The suspension was boiled for 20 hours. The supernatant was decanted from the polymer which was then washed several times with methanol and then dried. The infra-red spectrum of the resulting polymer was identical in all important respects with polyvinyl alcohol made in the conventional manner from polyvinyl acetate. The thermal properties of the polyvinyl alcohol were closely similar to those of the conventional polymer, as determined by differential thermal analysis.

EXAMPLE X The polymer of Example VIII and other similarly prepared by explosive polymerization were pooled to give 21 g. of polyDVC. They were boiled overnight with methanol containing 1 g. of dissolved sodium; the solution was decanted and fresh methanol containing 1 g. dissolved sodium was added and the suspension boiled for another 5 hr. The solvent was decanted and the product washed with methanol and dried, giving 8 g. of PVA, as shown by the infrared spectrum of this product. A clear, tough film was cast from a Water solution of this PVA. Since the initial polyDVC had about 50% of its carbonate groups in 5 memberd rings, the resultant PVA had 67% of its hydroxyl groups in 1,2-glycol units.

What is claimed is:

1. An addition homopolymer of a carbonate having the formula wherein R R and R are hydrogen, phenyl or alkyl containing up to 20 carbon atoms.

2. A polymer of a carbonate as defined in claim 1, wherein R R and R are hydrogen.

3. A polymer of a carbonate as defined in claim 1, wherein R is methyl in each case.

References Cited UNITED STATES PATENTS 2,370,589 2/ 1945 Strain et a1 260-775 2,410,305 10/1946 Richter et al 26077.5

OTHER REFERENCES Murahashi et al., Bull. Chem. Soc. Japan, vol. 38(11), November 1965, pp. 1905-1910.

SAMUEL H. BLECH, Primary Examiner US. Cl. X.R. 

